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Mechanochemistry-assisted synthesis of hierarchical porous carbons applied as supercapacitors

2017, Leistenschneider, Desirée, Jäckel, Nicolas, Hippauf, Felix, Presser, Volker, Borchardt, Lars

A solvent-free synthesis of hierarchical porous carbons is conducted by a facile and fast mechanochemical reaction in a ball mill. By means of a mechanochemical ball-milling approach, we obtained titanium(IV) citrate-based polymers, which have been processed via high temperature chlorine treatment to hierarchical porous carbons with a high specific surface area of up to 1814 m2 g−1 and well-defined pore structures. The carbons are applied as electrode materials in electric double-layer capacitors showing high specific capacitances with 98 F g−1 in organic and 138 F g−1 in an ionic liquid electrolyte as well as good rate capabilities, maintaining 87% of the initial capacitance with 1 M TEA-BF4 in acetonitrile (ACN) and 81% at 10 A g−1 in EMIM-BF4.

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Review: Carbon onions for electrochemical energy storage

2016, Zeiger, Marco, Jäckel, Nicolas, Mochalin, Vadym N., Presser, Volker

Carbon onions are a relatively new member of the carbon nanomaterials family. They consist of multiple concentric fullerene-like carbon shells which are highly defective and disordered. Due to their small size of typically below 10 nm, the large external surface area, and high conductivity they are used for supercapacitor applications. As electrode materials, carbon onions provide fast charge/discharge rates resulting in high specific power but present comparatively low specific energy. They improve the performance of activated carbon electrodes as conductive additives and show suitable properties as substrates for redox-active materials. This review provides a critical discussion of the electrochemical properties of different types of carbon onions as electrode materials. It also compares the general advantages and disadvantages of different carbon onion synthesis methods. The physical and chemical properties of carbon onions, in particular nanodiamond-derived carbon onions, are described with emphasis on those parameters especially important for electrochemical energy storage systems, including the structure, conductivity, and porosity. Although the primary focus of current research is on electrode materials for supercapacitors, the use of carbon onions as conductive additives and for redox-active species is also discussed.

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Vacuum or flowing argon: What is the best synthesis atmosphere for nanodiamond-derived carbon onions for supercapacitor electrodes?

2015, Zeiger, Marco, Jäckel, Nicolas, Weingarth, Daniel, Presser, Volker

We present a comprehensive study on the influence of the synthesis atmosphere on the structure and properties of nanodiamond-derived carbon onions. Carbon onions were synthesized at 1300 and 1700 °C in high vacuum or argon flow, using rapid dynamic heating and cooling. High vacuum annealing yielded carbon onions with nearly perfect spherical shape. An increase in surface area was caused by a decrease in particle density when transitioning from sp3 to sp2 hybridization and negligible amounts of disordered carbon were produced. In contrast, carbon onions from annealing nanodiamonds in flowing argon are highly interconnected by few-layer graphene nanoribbons. The presence of the latter improves the electrical conductivity, which is reflected by an enhanced power handling ability of supercapacitor electrodes operated in an organic electrolyte (1 M tetraethylammonium tetrafluoroborate in acetonitrile). Carbon onions synthesized in argon flow at 1700 °C show a specific capacitance of 20 F/g at 20 A/g current density and 2.7 V cell voltage which is an improvement of more than 40% compared to vacuum annealing. The same effect was measured for a synthesis temperature of 1300 °C, with a 140% higher capacitance at 20 A/g for argon flow compared to vacuum annealing.

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Sub-micron novolac-derived carbon beads for high performance supercapacitors and redox electrolyte energy storage

2016, Krüner, Benjamin, Lee, Juhan, Jäckel, Nicolas, Tolosa, Aura, Presser, Volker

Carbon beads with sub-micrometer diameter were produced with a self-emulsifying novolac–ethanol–water system. A physical activation with CO2 was carried out to create a high microporosity with a specific surface area varying from 771 (DFT) to 2237 m2/g (DFT) and a total pore volume from 0.28 to 1.71 cm3/g. The carbon particles conserve their spherical shape after the thermal treatments. The controllable porosity of the carbon spheres is attractive for the application in electrochemical double layer capacitors. The electrochemical characterization was carried out in aqueous 1 M Na2SO4 (127 F/g) and organic 1 M tetraethylammonium tetrafluoroborate in propylene carbonate (123 F/g). Furthermore, an aqueous redox electrolyte (6 M KI) was tested with the highly porous carbon and a specific energy of 33 W·h/kg (equivalent to 493 F/g) was obtained. In addition to a high specific capacitance, the carbon beads also provide an excellent rate performance at high current and potential in all tested electrolytes, which leads to a high specific power (>11 kW/kg) with an electrode thickness of ca. 200 μm.

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Electrospinning and electrospraying of silicon oxycarbide-derived nanoporous carbon for supercapacitor electrodes

2016, Tolosa, Aura, Krüner, Benjamin, Jäckel, Nicolas, Aslan, Mesut, Vakifahmetoglu, Cekdar, Presser, Volker

In this study, carbide-derived carbon fibers from silicon oxycarbide precursor were synthesized by electrospinning of a commercially available silicone resin without adding a carrier polymer for the electrospinning process. The electrospun fibers were pyrolyzed yielding SiOC. Modifying the synthesis procedure, we were able to obtain electrosprayed SiOC beads instead of fibers. After chlorine treatment, nanoporous carbon with a specific surface area of up to 2394 m2·g-1 was obtained (3089 m2·g-1 BET). Electrochemical characterization of the SiOC-CDC either as free-standing fiber mat electrodes or polymer-bound bead films was performed in 1 M tetraethylammonium tetrafluoroborate in acetonitrile (TEA-BF4 in ACN). The electrospun fibers presented a high gravimetric capacitance of 135 F·g-1 at 10 mV·s-1 and a very high power handling, maintaining 63 % of the capacitance at 100 A·g-1. Comparative data of SiOC-CDC beads and fibers show enhanced power handling for fiber mats only when the fiber network is intact, that is, a lowered performance was observed when using crushed mats that employ polymer binder.